Methods for the sustainable conversion of carbon dioxide to value-added chemical products are of technological and societal importance. Elegant advances in traditional approaches to CO2 reduction driven by electrical and/or solar inputs using homogeneous, heterogeneous, and biological catalysts point out key challenges in this area, namely: (i) the chemoselective conversion of CO2 to a single product while minimizing the competitive reduction of protons to hydrogen; (ii) long-term stability under environmentally friendly aqueous conditions; and (iii) unassisted light-driven CO2 reduction that does not require external electrical bias and/or sacrificial chemical quenchers. Synthetic homogeneous and heterogeneous CO2 catalysts are often limited by product selectivity and/or aqueous compatibility, whereas enzymes show specificity but are generally less robust outside of their protective cellular environment. In addition, the conversion of electrosynthetic systems to photosynthetic ones is nontrivial owing to the complexities of effectively integrating components of light capture with bond-making and bond-breaking chemistry.